Resist color printing



Inn!

?atented Oct. 15, 1940 UNITED STATES PATENT OFFICE RESIST COLOR PRDITING- Manchester,

N0 Drawing. Application January 18, 1938, Se-

rial No. 185,631. Ren

ewed January 3,1940. In

Great Britain January 21, 1937 3 Claims.

This invention relates to the production of resist efiects illuminated with vat dyestufis.

According to the invention I apply to a fabric composed wholly or partly of cellulosic fibre, for instance, cotton or viscose rayon, a vat dyestuff printing paste comprising, together with other usual ingredients, an organic isocyanate of the formula R-N=C=O in which R is a normal or branched chain saturated or unsaturated aliphatic hydrocarbon radical containing at least eight carbon atoms; I then steam the fabric, preferably after drying it and dye it with any suitable dyestufi to 'give colored patterns on a differently colored ground. The ground color is preferably applied by padding.

An example of a suitable compound of formula RN=C=O is heptadecylisocyanate. Alternatively there may be used, for example, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, cetyl, octadecyl, eikosyl, Z-ethylhexyl, 3-ethylnonyl or octadecenyl-isocyanate, likewise mixtures of isocyanates such as may be obtained from the mixed amines derived from the mixed acids obtained from coconut oil or stearin. These isocyanates may conveniently be prepared by the profess described in the specification of British Patent 485,761.

If desired, the said isocyanates may be used in conjunction with other known resist agents, for

example, gelatine, glue size, or other proteins or albumenoids.

It is convenient to employ the isocyanates in the form of aqueous emulsions or suspensions which may be produced, if desired, with the aid of an emulsifying agent such, for example, as a sulphated fatty alcohol.

As dyestuffs for providing the ground color I use vat dyestufis (applied either as such from reduction medium or in the soluble leuco ester form), azoic colors applied, for instance as ready-forprinting preparations of, e. g., diazoamino compound and coupling component, and mordant dyestufis.

In carrying the invention into practical effect it is preferable to workas far as possible at low temperatures, as by using cold padding liquors' and drying the fabric after padding by means of hot air rather than by passing it over heated cylinders. It is believed that the success of the process depends upon the production during the steaming operation (which also serves to fix the vat dyestufi on the fibre) of temporarily waterrepellent areas on the fabric where the printing paste has been applied. Such water-repellency would be impaired or destroyed by working at elevated temperatures.

Padding is preferably .done through the nip to minimise the time of contact of the fabric with the padding liquor.

As thickening agent there may be used, for example, British gum, starch-British gum, gum Senegal or gum Arabic.

The following examples, in which parts are by weight, serve to illustrate but do not limit the invention.

Example 1 A cellulosic fabric, for instance, cotton or viscose rayon, is printed in the usual way. with one of the following vat dyestuif printing pastes:

. Parts Parts Flavanthrone, 7% aqueous paste 10 Dimethoxydibenzanthrone 7% aqueous paste 10 Sodium formaldehyde sulphoxylate s 8 Potassium carbonate 13 13 Starch-British gum thickening 40 45 Zinc oxide powder 10 Heptadecylisocyanate. 4 4 Sodium eetylsulphate 0.2 0.2 Water 14.8 19.8

After printing it is dried, steamed at 100 C. for 5-20 minutes and nip-padded withone of the following solutions of leuco esters of vat dyestuffs:

Parts Parts Sulphuric ester ofleuco.dimethoxy-dibenzanthrone 12% aqueous paste Sulphuric ester of 6'6- thionaphthenindigo.

Tragacanth thickening 1:1...

Sodium nitrite 30% aqueous solution Water Solution A is employed with material which has been printed with the printing paste A, and solution B with material printed withthe paste B.

clear-cut green pattern on an orange ground.

Example 2 A cotton fabric is printed with one of the following vat dyestuff printing pastes:

The fabric is then dried, steamed at 100 C. for 5-20 minutes and padded in the following solution:

Parts Dimethoxydibenzanthrone '7 aqueous paste 1 Sodium formaldehyde sulphoxylate 5 Potassium carbonate 8 'Iragacanth thickening 1: 1 5 Water 81 The fabric is then dried, steamed, oxidised and soaped at the boil.

There is thus obtained a bright clear-cut yellow (A) or orange (3) pattern on a green ground.

Example 3 A cotton fabric isprinted with one of the following vat dyestufi' printing pastes:

- Parts Parts Flavanthrone 7% aqueous paste l0 Dimethoxydibenzanthrone, 7% aqueous past 10 Sodium formaldehyde sulphoxylate 8 8 Potassium carbonate 13 13 Starch-British gum thickening 1:1 45 45 He tadecylisocyanate 4 4 So ium cetyl sulphate- 0. 2 0. 2 Water l9. 8 l9. 8

The material is then dried and steamed as in Example 1, padded with one of the following:

An ice colour preparation containing a diazoimino compound from 4-benzoylamino-2z5-dietho aniline and Shydroxynaphthoic anilide, in t e usual commercial form as powder An ice colour preparation containing a diazoimino compound from 4-chloro-o-toluidine and B-hydrox aphthoic-o-toluidide, in the usual comm erc al form as 65% powder Sodium cetyl sulphate Caustic soda solution 90 Tw 'lragacanth thickening 1:1

Water Parts Solution A is used in conjunction with pasta A; solution B with paste B.

The fabric is then driedand developed by steaming for /2 hour in the presence of acetic and formic acid vapour and finally soaped at the boil. Treatment A gives a bright clear-cut yellow pattern on a blue ground; treatment B a bright clear-cut green pattern on a pink ground.

Example 4 A cotton fabric is first prepared with lowing coupling component solution:

the fol- The fabric is then dried, printed as in Example 2B, dried, steamed at 100 C. for 5-10 minutes and then padded with the following diazo solution:

Parts stabilised tetrazo compound from dianisidine (in its usual commercial form as 20% powder) ,3 Tragacanth thickening 1:1 5 Water 92 The material is then dried, washed and soaped at the boil. There is thus obtained a bright clearcut orange pattern on a blue ground.

Example 5 A cellulosic fabric (cotton or viscose rayon) is printed with a, vat dyestufi paste in the following composition:

Parts 6 6' -dichloro-2 :2 -bis-thionaphthen-indigo 12% aqueous paste Sodium formaldehyde sulphoxylate 8 Potassium carbonate 13 Starch-British gum thickening 1:1 45 Heptadecylisocyanate 2 Sodium cetyl sulphate 0.1 Water 23.9

The fabric is dried, steamed at 100 c. for 10 minutes and nip-padded with the following solution:

Parts a-Nitroso-p-naphthol as powder 2 Ferrous sulphate aqueous solution 21 Tw. 4 Tragacanth thickening 1:1 5 Water 89 It is then air-dried, immersed for 2 minutes in a boiling 2% solution of sodium carbonate, washed and soaped at the boil. There is thus obtained a bright clear-cut pink pattern on a green ground.

Example 6 A cotton fabric is printed with a dyestufi paste of the following composition:

Parts 5:7:5:7'-tetrabromoindigo 38% aqueous paste 4 Sodium formaldehyde sulphoxylate 8 Potassium carbonate 13 Starch-British gum thickening 1:1 45 Heptadecylisocyanate 2 Sodium cetyl sulphate 0.1 Water -1 27.9

Parts p-Hydroxynaphthoic anilide 1.5 Diacetone alcohol 1.5 Caustic soda solution Tw 1.5 Sodium cetyl sulphate 0.2 Water 95.3

The fabric is dried, steamed at 100 C. for 10 minutes and nip-padded with the following solution:

. Parts B-nitroalizarine 15% aqueous paste 2 Acetate of chrome liquor 28 Tw 8 Tragacanth thickening 1:1 5 Water It is then air-dried, steamed at 100 C. for &- hour, washed and soaped at the boil. There is thus obtained a bright clear-cut blue pattern on a brown ground.

Example 7 A cotton fabric is prepared by padding with a 1% solution of sodium nitrite, dried and printed as in Example 2B. After steaming at 100 C. for 5-10 minutes it is padded with the following ester salt solution:

Parts Sulphuric ester of leuco 16:17-diethylene ether of dihydroxy-dibenzanthrone 20% aqueous paste 3 Tragacanth thickening 1:1 5 Water 92 Example 8 Cotton fabric is printed and steamed as in Example 2B and is then padded in a liquor of the following composition:

Parts Dimethoxydibenzanthrone 7% aqueous paste 2 Caustic soda aqueous solution Tw 2 Sodium hydrosuIphite 2 Water 44 Tragacanth thickening 1 1 5 Water 45 In making up the liquor the first four ingredients are heated together until the dyestuif is completely dissolved. The solution is then cooled and the tragacanth' thickening and additional water (previously mixed) are added. a

The fabric is exposed to the air for /2-minute and then oxidised in the manner usual for vat dyestufis. It is finally soaped at the boil. There is thus obtained a bright clear-cut orange pattern on a green ground.

I claim:

1. A process for the production of resist effects illuminated with vat dyestuffs onfabrics composed wholly or partly'of cellulosic fiber which comprises applying to the said fabric a vat dyestuff printing paste containing an organic isocyanate of the formula R-N=C=O wherein R stands for an aliphatic hydrocarbon radical having at least eight carbon atoms, steaming the fabric, and applying to it another dyestufi to produce a differently colored ground.

2. A process as claimed in claim 1 in which the dyestufi used to provide the ground shade is one selected from the group consisting of another vat dyestuff, an azoic color, and a mordant dyestuif.

3. A process as claimed in claim 1 in which the organic isocyanate which is employed is heptadecyl isocyanate.

DENY S PERCIVAL MILBURN. 

